CN103572094A - Titanium alloy having good oxidation resistance and high strength at elevated temperatures - Google Patents

Titanium alloy having good oxidation resistance and high strength at elevated temperatures Download PDF

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CN103572094A
CN103572094A CN201310305783.XA CN201310305783A CN103572094A CN 103572094 A CN103572094 A CN 103572094A CN 201310305783 A CN201310305783 A CN 201310305783A CN 103572094 A CN103572094 A CN 103572094A
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oxidation
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engine
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CN103572094B (en
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孙福生
欧内斯特·M·克里斯
K·O·余
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Haomai aerospace Co.
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RTI International Metals Inc
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F01D25/005—Selecting particular materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion

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Abstract

A titanium alloy may be characterized by a good oxidation resistance, high strength and creep resistance at elevated temperatures up to 750 DEG C, and good cold/hot forming ability, good superplastic forming performance, and good weldability. The alloy may contain, in weight percent, aluminum 4.5 to 7.5, tin 2.0 to 8.0, niobium 1.5 to 6.5, molybdenum 0.1 to 2.5, silicon 0.1 to 0.6, oxygen up to 0.20, carbon up to 0.10, and balance titanium with incidental impurities.

Description

At high temperature there is good oxidation resistance and high-intensity titanium alloy
Cross
The application requires the right of priority of the U.S. Provisional Application that the sequence number of submission on July 19th, 2012 is 61/673,313, and the open mode by reference of above-mentioned application is incorporated at this.
Background technology
Because titanium alloy is used in aviation and other application widely, therefore the demand of the lighter titanium alloy of the weight of at high temperature using is constantly increased.For example, more the aircraft of high-performance and Geng Gao fuel efficiency and aircraft engine are just guiding the aircraft engine that operates under the condition of and weight saving higher in temperature and the development of fuselage.Thus, titanium alloy is considered to can be used for the hotter part compared with High Operating Temperature of bearing of nacelle or body parts, for example caudal hanger member.These development have caused with for example at 650 ℃, have the demand that excellent oxidation-resistance and high-intensity titanium alloy replace heavy nickel-base alloy (with other alloys) under 700 ℃ or 750 ℃ or higher high temperature.
For example the titanium alloy of Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Al-3Nb-0.2Si has been used to make and has required to have fuselage and the aircraft engine parts that oxidation-resistance, thermotolerance and quality are slim and graceful, and the oxidation resistance temperature of these alloys is limited to below 650 ℃ conventionally.There is the phenomenon of seriously peeling off in the parts that prolonged heat exposure can cause these two kinds of alloys to form at 700 ℃～750 ℃.In addition, rear a kind of alloy has obviously lower intensity when temperature reaches 700 ℃～750 ℃ under arms, and this is because it is near β titanium alloy.
Following recorded multiple titanium alloy provides the characteristic of various expectations, but they and inapplicable above-mentioned purpose.United States Patent (USP) 4,980,127 disclosed commercial titanium alloy T i-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si are the near β titanium alloys that molybdenum content is very high.United States Patent (USP) 4,738,822 is disclosed a kind of without niobium near αtitanium alloy Ti-6Al-2.7Sn-4Zr-0.4Mo-0.4Si, and it,, in the situation that temperature rising is quite high, has good intensity and creep resistance.United States Patent (USP) 4,906,436 and United States Patent (USP) 5,431,874 high-temperature titanium alloy that contains hafnium (Hf) and tantalum (Ta) is disclosed.
United States Patent (USP) 4,087,292 and United States Patent (USP) 4,770,726 disclose respectively two kinds of titanium alloy T i-5.5Al-3.5Sn-3Zr-1Nb-0.25Mo-0.3Si(containing niobium is called IMI829) and Ti-5.8Al-4Sn-3.5Zr-0.7Nb-0.5Mo-0.35Si-0.06C(be called IMI834), they at high temperature show good creep resistance.United States Patent (USP) 6,284,071 discloses a kind of high-temperature titanium alloy, and it contains 3.5% zirconium (Zr) and conventionally optionally up to 2.0% niobium (Nb).Before the titanium alloy of three patents comprise respectively and be no more than 1.25%, 1.5% and 2.0% niobium and at least 2.0%, 3.25% and 2.5% zirconium respectively.
It should be noted that being manufactured on the alloy under this high service temperature (especially at about 700 ℃, 750 ℃ or higher) with excellent oxidation-resistance is difficulty very.Therefore from the titanium alloy that can work 650 ℃, to the progress with good oxidation resistance and high-intensity titanium alloy that can work at 750 ℃, be for example, great leap.
This titanium alloy is effectively for this object or other objects, and the physical property of the multiple expectation except discussed above can be provided.
Summary of the invention
On the one hand, the present invention can provide a kind of high-temperature titanium alloy, and it mainly comprises: the aluminium of 4.5～7.5wt%; The tin of 2.0～8.0wt%; The niobium of 1.5～6.5wt%; The molybdenum of 0.1～2.5wt%; The silicon of 0.1～0.6wt%; With surplus titanium.
On the other hand, the present invention can provide a kind of high-temperature titanium alloy, comprising: the aluminium of 4.5～7.5wt%; The tin of 2.0-8.0wt%; The niobium of 1.5～6.5wt%; The molybdenum of 0.1～2.5wt%; The silicon of 0.1～0.6wt%; Zirconium and the vanadium of total content within the scope of 0.0～0.5wt%; And surplus titanium.
On the other hand, the present invention can provide a kind of method, comprises the following steps: a kind of parts that formed by titanium alloy are provided, and described titanium alloy by weight, mainly comprises: the aluminium of 4.5～7.5wt%; The tin of 2.0-8.0wt%; The niobium of 1.5～6.5wt%; The molybdenum of 0.1～2.5wt%; The silicon of 0.1～0.6wt%; With surplus titanium; The machine that operation comprises these parts, so that these parts are retained to continuously not a half hour at the temperature of at least 600 ℃.
Accompanying drawing explanation
Fig. 1 shows (a) this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si; (b) the titanium alloy T i-6Al-2Sn-4Zr-2Mo-0.1Si of prior art; (c) the titanium alloy T i-15Mo-3Nb-3Al-0.3Si of prior art, the view that there is no amplification of the oxidation sample after the oxidation of carrying out in air with 750 ℃ 208 hours is tested.
Fig. 2 shows (a) this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si; (b) the titanium alloy T i-6Al-2Sn-4Zr-2Mo-0.1Si(of prior art shows serious peeling off (flaking)); (c) the titanium alloy T i-15Mo-3Nb-3Al-0.3Si(of prior art shows peeling off of part), the view of scanning electronic microscope (SEM) that carries out 100 times of the surperficial amplifications of the oxidation sample after the oxidation test of 208 hours with 750 ℃ in air.
Fig. 3 shows that (a) this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si(shows as very closely, thin, continuous, polygonal zone of oxidation); (b) the titanium alloy T i-6Al-2Sn-4Zr-2Mo-0.1Si(of prior art shows as very porous, thick, lax, that come off and the subclavate zone of oxidation of class); (c) the titanium alloy T i-15Mo-3Nb-3Al-0.3Si(of prior art shows as zone of oxidation very porous, thick, lax and like fibrous shape), with 750 ℃, in air, carry out the view of scanning electronic microscope (SEM) of 10000 times of amplifications of the zone of oxidation of the oxidation sample after the oxidation test of 208 hours.
Fig. 4 shows the titanium alloy T i-6Al-2Sn-4Zr-2Mo-0.1Si of (a) prior art, (b) the titanium alloy T i-6Al-6Zr-6Nb-0.5Mo-0.3Si of prior art, (c) the titanium alloy T i-6Al-2Sn-4Zr-6Nb-0.5Mo-0.3Si(d of prior art) the exemplary titanium alloy T i-6Al-6Sn-6Nb-0.5Mo-0.3Si of the present invention and (e) microgram of the exemplary titanium alloy T i-6Al-6Sn-4Nb-0.5Mo-0.3Si of the present invention.
Fig. 5 is the stereographic map of aircraft, and it illustrates the engine being arranged on aircraft wing.
Fig. 6 is the amplification profile along 6-6 line of Fig. 5, and it shows each member of aircraft engine, hanger and wing.
Fig. 7 is the stereographic map that each fastening piece or clamp structure are shown.
Fig. 8 is the view elevation view of automotive engine valves.
Embodiment
In general, exemplary alloy of the present invention can comprise or mainly consist of the following composition: aluminium (Al): about 4.5～7.5wt%, tin (Sn): about 2.0～8.0wt%, niobium (Nb): about 1.5～6.5wt%; Molybdenum (Mo): about 0.1～2.5wt%, silicon (Si): about 0.1～0.6wt%, and there is the even titanium (Ti) of the surplus of impurity of depositing.The per-cent of other various elements that this alloy may comprise will be discussed in detail below.Have been found that and above-mentioned in hexagonal structure titanium, add Al, Sn, Nb, Mo and Si and both can make oxidation-resistance be greatly improved, can significantly strengthen again the intensity under 750 ℃ or higher temperature.
The oxidation-resistance of the obvious improvement of this titanium alloy mainly obtains by common interpolation Nb and Sn.This is owing to using Nb and Sn can form very fine and close, thin and continuous, polygonal zone of oxidation in alloy, as amplifies as shown in Fig. 3 of 10000 times.Oxide protective layer provides and can reduce oxygen to the barrier of titanium matrix internal diffusion, and the thermal stresses between zone of oxidation and titanium is reduced to minimum to eliminate the phenomenon of spalling of oxide layer.On the contrary, in amplifying respectively Fig. 3 b and the Ti-6Al-2Sn-4Zr-2Mo-0.1Si shown in Fig. 3 c and Ti-15Mo-3Nb-3Al-0.3Si of 10000 times, can observe porous, thick and loose, that come off, irregularly shaped (shaft-like or be fibrous) zone of oxidation.
The oxidation-resistance of titanium alloy can be peeled off to represent by α phase layer depth, weightening finish and layer.α mutually layer is the oxygen-rich layer being positioned at below zone of oxidation, and it is the layer being highly brittle, and can obviously reduce the mechanical characteristics of titanium, as ductibility and fatigue strength.So, the formation of opposing α phase layer has just represented that titanium alloy has better oxidation-resistance.Therefore, relatively little α phase layer depth (or degree of depth of α phase layer) represents that titanium alloy has oxidation-resistance relatively preferably.
As shown in the various titanium alloys of testing in table 4 and Fig. 4, exemplary alloy of the present invention, Ti-6Al-6Sn-6Nb-0.5Mo-0.3Si(Fig. 4 d for example) and Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si(Fig. 4 e) not only show minimum weightening finish, also show minimum α phase layer depth.Under equal experiment condition, the α phase layer depth of exemplary alloy of the present invention be only Ti-6Al-2Sn-4Zr-2Mo-0.1Si(Fig. 4 a) about 50%.For example, although the relative exemplary alloy of the present invention of titanium alloy (Ti-6Al-6Zr-6Nb-0.5Mo-0.3Si as shown in Figure 4 b and the Ti-6Al-2Sn-4Zr-6Nb-0.5Mo-0.3Si shown in Fig. 4 c) (Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si shown in the Ti-6Al-6Sn-6Nb-0.5Mo-0.3Si shown in Fig. 4 d and Fig. 4 e) containing zirconium is having slight growth aspect weightening finish, front a kind of alloy (containing Zr and Nb) shows as the twice of the α phase layer depth that is exemplary alloy of the present invention (containing Sn and Nb).Studies have shown that and can observe serious peeling phenomenon containing in the titanium alloy of zirconium.
The oxidation-resistance aspect that zirconium is found in titanium alloy has significant negative effect.Therefore, the good oxidation-resistance of this alloy is by providing a kind of titanium alloy composition of the zirconium that does not substantially contain zirconium or comprise minimum to realize, as further described in detail below to a certain extent.So, zirconium is not that the part as alloy composite is added wittingly conventionally, and any zirconium is normally present in alloy as impurity.
Alloy of the present invention is different from known existing commercial high-temperature titanium alloy, the titanium alloy of for example discussing in the application's background technology.For oxidation-resistance, hot strength and creep resistance, alloy of the present invention is far away higher than commercial Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si.Rear a kind of alloy is the near β titanium alloy that molybdenum content is very high, so this alloy of it and the common near αtitanium alloy that adds Nb and Sn is completely different.
Although Ti-6Al-2.7Sn-4Zr-0.4Mo-0.4Si is the near αtitanium alloy simultaneously with good hot strength and creep resistance, this alloy does not contain niobium and its oxidation-resistance lower than this alloy.This alloy is also different from United States Patent (USP) 4,906,436 and United States Patent (USP) 5,431,874 in alloy, they disclose the high-temperature titanium alloy that contains hafnium and tantalum separately.
This alloy is also different from the following high-temperature titanium alloy containing niobium.As the application's background technology is recorded, United States Patent (USP) 4,087,292, United States Patent (USP) 4,770,726 and United States Patent (USP) 6,284,071 disclose respectively the titanium alloy that contains zirconium and relative low-level niobium.As mentioned above, zirconium is found at high temperature to make the oxidation-resistance of titanium greatly degenerate.In addition, jointly add the niobium of low levels and the zirconium of high-content can cause the at high temperature very dark and serious peeling phenomenon of α phase layer.
Therefore, alloy designs of the present invention is for added the titanium alloy without zirconium or essentially no zirconium of tin and high-content niobium (being preferably 3.0～6.0%) simultaneously.In addition, this alloy shows than the better oxidation-resistance of alloy of three patents above.
Alloy designs of the present invention is near αtitanium alloy.The close-packed six side α phases that its main matrix phase is titanium.Its strengthening is to realize by element aluminum, tin, niobium, molybdenum, silicon, and its oxidation-resistance is by jointly adding niobium and Xi Lai to improve.
The content of aluminium generally should be high as much as possible, to obtain the maximum strengthening of α phase, and avoids intermetallic compound (Ti 3al) formation.Adding aluminium is effective improving aspect hot strength and creep resistance.For realizing this effect, it is necessary adding at least 4.5% aluminium, yet the aluminium of too high amount can cause fragility Ti 3the formation of Al phase; Therefore, aluminium content should be restricted at the most 7.5%.
Tin is very effective element improving aspect oxidation-resistance after jointly adding niobium.Generally speaking, the content of tin is higher, and oxidation-resistance is better.Tin has also been strengthened α phase and β phase simultaneously, and is effective improving aspect hot strength.Add 2.0% or more tin improving aspect oxidation-resistance and intensity, be preferred.Yet excessive tin content can cause fragility Ti 3the formation of Al phase, and reduce ductibility and weldability.Therefore the maximum level of tin should be controlled at and be no more than 8.0%.
Niobium is very important element significantly improving aspect oxidation-resistance after jointly adding tin.When alloy is heated to high temperature, jointly add niobium and tin can cause very dense, thin, continuous and polygonal zone of oxidation.Add niobium also can make thermal stresses between zone of oxidation and titanium matrix reduce to minimum, thereby eliminate Long Time Thermal, be exposed to peeling off of zone of oxidation after high temperature.Add 1.5% or more niobium improving in oxidation-resistance, be preferred; Yet niobium is weak β phase stabilizer, and mainly strengthen β phase.Add in large quantities niobium will introduce more β phase, and therefore reduce hot strength and creep resistance.Therefore, the upper limit of niobium should be 6.5%, comprises 1.5 to 6.5% niobium at this this alloy, and for example can comprise 2.0,2.5 or 3.0% to 4.5,5.0,5.5,6.0 or 6.5% niobium.In one exemplary embodiment, this alloy can comprise 2.5 to 3.5% to 2.75 to 3.25% niobium.
Tantalum be can also in alloy, add and oxidation-resistance and hot strength improved.The upper limit of tantalum should be 1.0%, and therefore in the scope of 0.0-1.0wt%.
Molybdenum is stronger β stablizer, and mainly strengthens β phase.A small amount of molybdenum (0.5%) will strengthen the tensile strength of this alloy.A large amount of molybdenums will reduce creep resistance.Therefore, adding of molybdenum should be in the scope of 0.1-2.5%.
Silicon forms titanium silicide at crystal boundary and matrix place conventionally.Silicon can be added in this alloy, for improving creep resistance.Adding of silicon is the scope 0.1 to 0.6%, and under this scope, the effect of silicon aspect creep resistance is obvious.
Preferably the oxygen level in this titanium alloy is controlled, because it is strong alpha stabilizers.Excessive oxygen level is easy to reduce ductility and the fracture toughness property after heat exposes.The upper limit of oxygen is 0.20%, is preferably 0.12%.Oxygen is conventionally in the scope of 0.08～0.20wt% or 0.08～0.12wt%.Carbon in this alloy is also conventionally controlled in and is no more than 0.10%, and conventionally in the scope of 0.02～0.10wt% or 0.02～0.04wt%.
They in this alloy, are preferably left out or two kinds of elements that content is very limited are zirconium and vanadium, because can reduce oxidation-resistance.Their the combination upper limit should be controlled at and be no more than 0.5wt%.Zirconium and vanadium amount is separately preferably in the scope of 0.0～0.5wt%, but the total amount of zirconium and vanadium is also preferably in the scope of 0.0～0.5wt%.
For improving hot strength and creep resistance, elemental nickel, iron, chromium, copper and manganese in this alloy, should be excluded or content very limited; These elements are controlled in respectively and are no more than 0.10wt%, and total residual element content of combination is controlled in and is no more than 0.30wt%.Therefore, in this alloy, these five kinds of elements content separately can be preferably in the scope of 0.0～0.10wt%, and the total amount of these five kinds of elements is preferably in the scope of 0.0～0.30wt%.
Element hafnium and rhenium in this titanium alloy, be excluded or content very limited.Their the combination upper limit should be controlled in and be no more than 0.3wt%.Therefore, in this alloy, hafnium and rhenium amount is separately preferably in the scope of 0.0～0.3wt%, but the total amount of hafnium and rhenium is also in the scope of 0.0～0.3wt%.
This titanium alloy is conventionally no longer included in this element is in addition discussed, unless they are on the impact that provides the object of the titanium alloy at high temperature with oxidation-resistance, intensity and creep resistance discussing in detail at this not produce or only produce minimum degree.
First technic metal is molten into 250-gm button-type (button), and is rolled into 0.100 " (being about 2.54 millimeters) thick lamella, then heat-treat.Al, Sn, Zr, Nb, Mo and Si are studied in the oxidation-resistance of titanium alloy and the effect aspect mechanical property.Based on experimental result, have that to demarcate composition be that two kinds of alloys of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si and Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si are selected for and amplify research.The ingot bar of four 70 kilograms is melted by use plasma arc melting technology, then at β, is rolled into plate mutually in field, then at alpha+beta, is rolled into the 0.135x31.5x100 inch lamella of (being about 3.43x800.1x2540 millimeter) mutually in field.Under differing temps, lamella is heat-treated, to make three kinds of microstructures: bimodal I(15% primary α (primary alpha)), bimodal II(35% primary α), and etc. axle microstructure (60% primary α).Aspect tensile property to lamella after oxidation-resistance, tensile property, creep resistance breaking property, heat expose, cold/thermoforming, superplastic forming test and weldability, assess.
Table 1 and table 5 provided after substantially invariable time cycle or time length given in continuing to be exposed to air to sample under fixed temperature, the weightening finish (mg/cm of various titanium alloy samples 2).Table 1 and table 5 provide a kind of measurement mode of indicating the oxidation-resistance of various titanium alloys.It ought be respectively that 650,700 and 750 ℃ (being respectively 1202,1292 and 1382 °F) continue 24,48,72,96 respectively to fixed temperature that table 1 provides, after 160 and 208 hours, and the comparison of increasing weight between this alloy sample and other titanium alloys.Especially, other titanium alloys in table 1 are commercial alloy Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si, and titanium alloy of the present invention in table 1 is Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si and Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si.
Table 5 more particularly shows above-mentioned three kinds of microstructures of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy in each identical temperature and the weightening finish under the time length.As shown in table 1, this exemplary alloy shows the oxidation-resistance that is far longer than commercialization alloy Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si.Three kinds of microstructures of this exemplary alloy are compared other alloys and are shown as and only have relatively slight weightening finish under similarity condition.This good combination for excellent oxidation-resistance and different mechanical property grade provides the selection of different microstructure.Except specific microstructure, this exemplary alloy shows as the oxidation-resistance that is far superior to described commercial exemplary alloy.
In the test implementation example of this titanium alloy, weightening finish (mg/cm 2) be: for example, at about 650 ℃, continue to remain on air in after 24 hours, be no more than 0.08,0.09,0.10,0.11,0.12,0.13,0.14 or 0.15, continue to remain on air at about 650 ℃ in, after 48 hours, be no more than 0.11,0.12,0.13,0.14,0.15,0.16,0.17,0.18,0.19 or 0.20, continue to remain on air at about 650 ℃ in, after 72 hours, be no more than 0.13,0.14,0.15,0.16,0.17,0.18,0.19,0.20,0.21 or 0.22, continue to remain on air at about 650 ℃ in, after 96 hours, be no more than 0.14,0.15,0.16,0.17,0.18,0.19,0.20,0.21,0.22,0.23,0.24 or 0.25, continue to remain on air at about 650 ℃ in, after 160 hours, be no more than 0.18,0.19,0.20,0.21,0.22,0.23,0.24,0.25,0.26,0.27,0.28,0.29 or 0.30, continue to remain on air at about 650 ℃ in, after 208 hours, be no more than 0.20,0.21,0.22,0.23,0.24,0.25,0.26,0.27,0.28,0.29,0.30,0.31,0.32,0.33,0.34 or 0.35, continue to remain on air at about 700 ℃ in, after 24 hours, be no more than 0.17,0.18,0.19,0.20,0.21,0.22,0.23,0.24,0.25,0.26 or 0.27, continue to remain on air at about 700 ℃ in, after 48 hours, be no more than 0.23,0.24,0.25,0.26,0.27,0.28,0.29,0.30,0.31,0.32,0.33,0.34 or 0.35, continue to remain on air at about 700 ℃ in, after 72 hours, be no more than 0.28,0.29,0.30,0.31,0.32,0.33,0.34,0.35,0.36,0.37,0.38,0.39,0.40,0.41,0.42,0.43,0.44 or 0.45, continue to remain on air under about 700 ℃ of C in, after 96 hours, be no more than 0.32,0.33,0.34,0.35,0.36,0.37,0.38,0.39,0.40,0.41,0.42,0.43,0.44,0.45,0.46,0.47,0.48,0.49 or 0.50, continue to remain on air at about 700 ℃ in, after 160 hours, be no more than 0.42,0.43,0.44,0.45,0.46,0.47,0.48,0.49,0.50,0.51,0.52,0.53,0.54,0.55,0.56,0.57,0.58,0.59 or 0.60, continue to remain on air at about 700 ℃ in, after 208 hours, be no more than 0.47,0.48,0.49,0.50,0.51,0.52,0.53,0.54,0.55,0.56,0.57,0.58,0.59,0.60,0.61,0.62,0.63,0.64,0.65,0.66,0.67,0.68,0.69,0.70,0.71,0.72,0.73,0.74,0.75,0.76,0.77,0.78,0.79 or 0.80, continue to remain on air at about 750 ℃ in, after 24 hours, be no more than 0.35,0.36,0.37,0.38,0.39,0.40,0.41,0.42,0.43,0.44,0.45,0.46,0.47,0.48,0.49,0.50,0.51,0.52,0.53,0.54,0.55,0.56,0.57,0.58,0.59 or 0.60, continue to remain on air at about 750 ℃ in, after 48 hours, be no more than 0.49,0.50,0.51,0.52,0.53,0.54,0.55,0.56,0.57,0.58,0.59,0.60,0.61,0.62,0.63,0.64,0.65,0.66,0.67,0.68,0.69or0.70,0.71,0.72,0.73,0.74,0.75,0.76,0.77,0.78,0.79 or 0.80, continue to remain on air at about 750 ℃ in, after 96 hours, be no more than 0.72,0.73,0.74,0.75,0.76,0.77,0.78,0.79,0.80,0.81,0.82,0.83,0.84,0.85,0.86,0.87,0.88,0.89,0.90,0.91,0.92,0.93,0.94,0.95,0.96,0.97,0.98,0.99,1.00,1.01,1.02,1.03,1.04,1.05,1.06,1.07,1.08,1.09,1.10,1.10,1.11,1.12,1.13,1.14,1.15,1.16,1.17,1.18,1.19 or 1.20, continue to remain on air at about 750 ℃ in, after 160 hours, be no more than 0.95,0.96,0.97,0.98,0.99,1.00,1.01,1.02,1.03,1.04,1.05,1.06,1.07,1.08,1.09,1.10,1.10,1.11,1.12,1.13,1.14,1.15,1.16,1.17,1.18,1.19,1.20,1.21,1.22,1.23,1.24,1.25,1.26,1.27,1.28,1.29,1.30,1.30,1.31,1.32,1.33,1.34,1.35,1.36,1.37,1.38,1.39,1.40,1.41,1.42,1.43,1.44,1.45,1.46,1.47,1.48,1.49 or 1.50, and, continue to remain on air at about 750 ℃ in after 208 hours, be no more than 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70 or 2.00.
Table 4 shows weightening finish and the α phase layer depth of each alloy after specific oxidation test.More specifically, this exemplary alloy Ti-6Al-6Sn-6Nb-0.5Mo-0.3Si(Fig. 4 d) at about 750 ℃, continue to remain on air in after 208 hours, there is the α phase layer depth that is no more than about 80,85,90,95 or 100 microns (μ m); And, at about 650 ℃, continue to remain on air in after 208 hours, there is the α phase layer depth that is no more than about 40,45,50 or 55 microns.In addition, this exemplary alloy Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si(Fig. 4 e) at about 750 ℃, continue to remain on air in after 208 hours, have be no more than about 70,75,80,85, the α phase layer depth of 90,95 or 100 microns; And, at about 650 ℃, continue to remain on air in after 208 hours, there is the α phase layer depth that is no more than about 20,25,30,35,40,45,50 or 55 microns.
Table 2 and table 6 show the tensile property of each titanium alloy sample---ultimate tensile strength, yield strength and percentage elongation.Table 2 provides about 25,200,400,600,650, under 700and750 ℃ (being respectively 77,392,752,1112,1202,1292 and 1382 °F), and the comparison of tensile property between other titanium alloys of this alloy sample box.Especially, other titanium alloys in table 2 are commercial alloy Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si, and this titanium alloy in table 2 is Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si and Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si.Fig. 6 shows above-mentioned three kinds of microstructures tensile property on longitudinal direction (L-dir) and transverse direction (T-dir) under same temperature condition of this exemplary alloy Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si.
The ultimate tensile strength (UTS) of the testability embodiment of this titanium alloy is at least 1100,1110 at the temperature of about 25 ℃, 1120,1130,1140,1150,1160,1170,1180,1190,1200,1210,1220 or 1230 MPas (MPa); At the temperature of about 200 ℃, be at least 880,890,900,910,920,930,940,950,960,970,980,990,1000,1010,1020,1030 or 1040 MPas; At the temperature of about 400 ℃, be at least 760,770,780,790,800,810,820,830,840,850,860,870,880,890,900 or 910 MPas; At the temperature of about 600 ℃, be at least 590,600,610,620,630,640,650,660,670,680,690,700 or 710 MPas; At the temperature of about 650 ℃, be at least 480,490,500,510,520,530,540,550,560,570,580,590,600,610 or 620 MPas; At the temperature of about 700 ℃, be at least 380,390,400,410,420,430,440,450,460,470,480,490,500,510 or 520 MPas; And be at least 260,270 at the temperature of about 750 ℃, 280,290,300,310,320,330,340,350,360,370,380,390,390 or 400 MPas.
The yield strength (YS) of the testability embodiment of this titanium alloy is at least 1000,1010 at the temperature of about 25 ℃, 1020,1030,1040,1050,1060,1070,1080,1090,1100,1110,1120,1130,1140,1150,1160 or 1170 MPas (MPa); At the temperature of about 200 ℃, be at least 750,760,770,780,790,800,810,820,830,840,850,860,870,880,890 or 900 MPas; At the temperature of about 400 ℃, be at least 600,610,620,630,640,650,660,670,680,690,700,710,720,730,740,750,760,770 or 780 MPas; At the temperature of about 600 ℃, be at least 460,470,480,490,500,510,520,530,540 or 550 MPas; At the temperature of about 650 ℃, be at least 370,380,390,400,410,420,430,440,450,460,470 or 480 MPas; At the temperature of about 700 ℃, be at least 250,260,270,280,290,300,310,320,330,340,350 or 360 MPas; And be at least 150,160 at the temperature of about 750 ℃, 170,180,190,200,210,220,230,240,250,260 or 270 MPas.
Table 3 and 7 shows the creep rupture character of each titanium alloy.Table 3 shows this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si and the Ti-6Al-6Sn-3Nb-0.5Mo-0.3Si creep fracture time under the condition of 650 ℃ and 138MPa and is far longer than commercial alloy Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si.Table 7 shows for this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si, and aforesaid bimodal I microstructure creep fracture time on longitudinal direction under 600 ℃ and 173MPa is at least about 90,95 or 100 hours; Under 650 ℃ and 138MPa, it is at least about 90,95 or 100 hours; Under 700 ℃ and 104MPa, it is at least about 30,35,40 or 45 hours; And under 750 ℃ and 69MPa, it is at least 10,15,20 or 25 hours.Table 7 also shows for this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si, and aforesaid bimodal II microstructure creep fracture time on longitudinal direction under 600 ℃ and 173MPa is at least about 90,95 or 100 hours; Under 650 ℃ and 138MPa, be at least about 50,55,60,65,70 or 75 hours; Under 700 ℃ and 104MPa, it is at least about 5 or 10 hours; And under 750 ℃ and 69MPa, it is at least 5,10 or 15 hours.Table 7 further shows for this exemplary titanium alloy T i-6Al-4Sn-3Nb-0.5Mo-0.3Si, and the aforesaid axle microstructure that waits is under 650 ℃ and 138MPa, and the creep fracture time on longitudinal direction is at least about 5,10,15 or 20 hours.
Alloy of the present invention can be heat-treated to obtain the microstructure of target, is at least reaching high strength under the high temperature of 750 ℃ and good creep rupture character, and keep good ductility thereby optimize.When solid solubility temperature increases, the volume fraction of primary α can decline, and therefore causes high strength and high creep resistance at high temperature.
In some applications, it may be important that alloy of the present invention at high temperature keeps deformation resistance during life-time service, and alloy may be also important continuing to keep enough room temperature ductility after heat exposes.This is called as heat and exposes rear stability.After table 8 shows at 650,700 and 750 ℃ heat and exposes 100 hours, the room temperature of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si (about 25 ℃) tensile property.Sample is carrying out having removed zone of oxidation before Elongation test.This alloy shows good room temperature ductility and intensity, and this shows that this alloy has the stability after good heat exposes when the depositing mutually of unharmful and fragility.
The effect of zone of oxidation aspect room temperature (about 25 ℃) tensile property is as shown in table 9.After at 650,700 and 750 ℃, heat exposes 100 hours, to the sample test that stretches of all zone of oxidation.Clearly, this alloy demonstrates good room temperature strength and enough ductility or 2～4% percentage elongation.Especially it should be noted that this exemplary titanium alloy heat under the high temperature of 750 ℃ exposes room temperature tensile ductility or the percentage elongation after 100 hours.On the contrary, commercial Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-6Al-2Sn-4Zr-2Mo-0.1Si alloy show serious spalling of oxide layer under the high temperature of 750 ℃, make it lose stretching ductility, or make material crisp to obtaining yield strength.
Usually reference table 8, the Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal I microstructure continues heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, room temperature (about 25 ℃) ultimate tensile strength (UTS) is at least about 1100,1110,1120,1130,1140 or 1150MPa; Remove zone of oxidation about 700 ℃ continue heat and expose 100 hours after, be at least about 1100,1110,1120,1130 or 1140MPa; And remove zone of oxidation about 750 ℃ continue heat and expose 100 hours after, be at least about 1050,1060,1070,1080 or 1090MPa.The Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal II microstructure continues heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, room temperature ultimate tensile strength (UTS) is at least about 1070,1080,1090,1100,1110 or 1120MPa; Remove zone of oxidation about 700 ℃ continue heat and expose 100 hours after, be at least about 1080,1090,1100,1110 or 1120MPa; And remove zone of oxidation about 750 ℃ continue heat and expose 100 hours after, be at least about 1050,1060,1070,1080 or 1090MPa.There is the aforesaid Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si of axle microstructure that waits and continue heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, room temperature ultimate tensile strength (UTS) is at least about 1170,1180,1190,1200,1210 or 1220MPa; Remove zone of oxidation about 700 ℃ continue heat and expose 100 hours after, be at least about 1100,1110,1120,1130,1140 or 1150MPa; And remove zone of oxidation about 750 ℃ continue heat and expose 100 hours after, be at least about 1100,1110,1120,1130,1140,1150,1160 or 1170MPa.
Continue reference table 8, the Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal I microstructure continues heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, and room temperature yield strength (YS) is at least about 1040,1050,1060,1070 or 1080MPa; Remove zone of oxidation about 700 ℃ continue heat and expose 100 hours after, be at least about 1000,1010,1020,1030,1040,1050,1060 or 1070MPa; And remove zone of oxidation about 750 ℃ continue heat and expose 100 hours after, be at least about 970,980,990,1000 or 1010MPa.The Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal II microstructure is after removing and continuing heat at about 650 ℃ of zone of oxidation and expose 100 hours, and room temperature yield strength (YS) is at least about 1040,1050,1060,1070 or 1080MPa; Remove zone of oxidation about 700 ℃ continue heat and expose 100 hours after, be at least about 1000,1010,1020,1030,1040,1050 or 1060MPa; And remove zone of oxidation about 750 ℃ continue heat and expose 100 hours after, be at least about 980,990,1000,1010 or 1020MPa.Have the aforesaid Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si that waits axle microstructure after removing and continuing heat at about 650 ℃ of zone of oxidation and expose 100 hours, room temperature yield strength (YS) is at least about 1130,1140,1150,1160,1170 or 1180MPa; Remove zone of oxidation about 700 ℃ continue heat and expose 100 hours after, be at least about 1040,1050,1060,1070,1080,1090 or 1100MPa; And remove zone of oxidation about 750 ℃ continue heat and expose 100 hours after, be at least about 1050,1060,1070,1080,1090,1100 or 1110MPa.
Continue reference table 8, the Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal I microstructure continues heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, and room temperature percentage elongation (El., %) is at least about 10,11,12,13 or 14; At about 700 ℃ that remove zone of oxidation, continuing heat exposure after 100 hours, is at least about 10,11,12,13 or 14; And at about 750 ℃ that remove zone of oxidation, continuing heat exposure after 100 hours, is at least about 10,11,12,13 or 14.The Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal II microstructure continues heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, and room temperature percentage elongation is at least about 10,11,12,13,14 or 15; At about 700 ℃ that remove zone of oxidation, continuing heat exposure after 100 hours, is at least about 10,11,12,13 or 14; And at about 750 ℃ that remove zone of oxidation, continuing heat exposure after 100 hours, is at least about 10,11,12,13,14 or 15.Have the aforesaid Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si of axle microstructure that waits and continue heat exposure after 100 hours at about 650 ℃ of removal zone of oxidation, room temperature percentage elongation is at least about 7,8,9,10 or 11; At about 700 ℃ that remove zone of oxidation, continuing heat exposure after 100 hours, is at least about 7,8,9,10 or 11; And at about 750 ℃ that remove zone of oxidation, continuing heat exposure after 100 hours, is at least about 7,8,9,10,11 or 12.
Usually reference table 9, the Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal I microstructure continued heat exposure after 100 hours at about 650 ℃ in specimen in reservation zone of oxidation, room temperature (about 25 ℃) ultimate tensile strength (UTS) is at least about 1090,1100,1110,1120,1130 or 1140MPa; Retain zone of oxidation in specimen about 700 ℃ continue heat and expose 100 hours after, be at least about 1080,1090,1100,1110 or 1120MPa; And retain zone of oxidation in specimen about 750 ℃ continue heat and expose 100 hours after, be at least about 1020,1030,1040,1050 or 1060MPa.The Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal II microstructure continued heat exposure after 100 hours at about 650 ℃ in specimen in reservation zone of oxidation, room temperature ultimate tensile strength (UTS) is at least about 1070,1080,1090,1100,1110,1120 or 1130MPa; Retain zone of oxidation in specimen about 700 ℃ continue heat and expose 100 hours after, be at least about 1040,1050,1060,1070 or 1080MPa; And retain zone of oxidation in specimen about 750 ℃ continue heat and expose 100 hours after, be at least about 1000,1010,1020,1030,1040 or 1050MPa.
Continue reference table 9, the Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal I microstructure continued heat exposure after 100 hours at about 650 ℃ in specimen in reservation zone of oxidation, room temperature yield strength (YS) is at least about 1040,1050,1060,1070,1080,1090 or 1100MPa; Retain zone of oxidation in specimen about 700 ℃ continue heat and expose 100 hours after, be at least about 1000,1010,1020,1030,1040,1050,1060or1070MPa; And retain zone of oxidation in specimen about 750 ℃ continue heat and expose 100 hours after, be at least about 970,980,990,1000 or 1010MPa.The Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal II microstructure continued heat exposure after 100 hours at about 650 ℃ in specimen in reservation zone of oxidation, room temperature yield strength (YS) is at least about 1040,1050,1060,1070,1080 or 1090MPa; Retain zone of oxidation in specimen about 700 ℃ continue heat and expose 100 hours after, be at least about 990,1000,1010,1020 or 1030MPa; And retain zone of oxidation in specimen about 750 ℃ continue heat and expose 100 hours after, be at least about 970,980,990,1000 or 1010MPa.
Continue reference table 9, the Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal I microstructure continued heat exposure after 100 hours at about 650 ℃ in specimen in reservation zone of oxidation, and room temperature percentage elongation (El., %) is at least about 1,2 or 3; Retaining the about 700 ℃ lasting heat exposures of zone of oxidation in specimen after 100 hours, be at least about 1,2 or 3; And retaining the about 750 ℃ lasting heat exposures of zone of oxidation in specimen after 100 hours, be at least about 1,2 or 3.The Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si with aforesaid bimodal II microstructure continued heat exposure after 100 hours at about 650 ℃ in specimen in reservation zone of oxidation, room temperature percentage elongation is at least about 1,2 or 3; Retaining the about 700 ℃ lasting heat exposures of zone of oxidation in specimen after 100 hours, be at least about 1,2,3 or 4; And retaining the about 750 ℃ lasting heat exposures of zone of oxidation in specimen after 100 hours, be at least about 1,2 or 3.
This alloy is at room temperature highly shapable (cold shaping ability), or is at high temperature highly shapable (thermoforming ability).Table 10 shows the hyperbolic test data of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si.As nearly α alloy, the ratio that this alloy can carry out radius/thickness is 2.6,2.7,2.8,2.9,3.0,3.1,3.2,3.3,3.4,3.5, cold shaping under 3.6,3.7,3.8,3.9 or 4.0, is starkly lower than the ratio of radius/thickness of Ti-6Al-2Sn-4Zr-2Mo-0.1Si desired 4.5.Table 11 shows the strain rate effect rate stretching result of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si at approximately 780 ℃ to approximately 930 ℃.This alloy shows good thermoforming ability, at high temperature has very high ductility or percentage elongation (approximately 90% to 230% elongation) and enough low mobility stress.
Alloy of the present invention can also be by being used superplastic forming (SPF) technique to form the parts of complicated shape.Table 12 shows in the temperature range of 925 ℃ to 970 ℃, and Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si is at 3x10 -4superplastic forming character under the strain rate of/second.This alloy shows the elongation of 340%-460%, and the enough low mobility stress being shaped for SPF.It is welding titanium alloy that this test also illustrates this alloy, because it is near αtitanium alloy.
From the data of introducing above, can see, the invention provides a kind of high-temperature oxidation resistant titanium alloy, it can use under at least up to the high temperature of 750 ℃.Alloy phase ratio of the present invention is as the commercial alloy of Ti-6Al-2Sn-4Zr-2Mo-0.1Si and Ti-15Mo-3Nb-3Al-0.3Si, not only at high temperature there is high strength, and have larger oxidation-resistance, and it shows the good over-all properties of the stability after excellent oxidation-resistance, the high strength under high temperature and creep resistance and heat exposure.In addition, this alloy can be by being used the method for cold shaping, thermoforming, superplastic forming and welding technique to manufacture parts.
These character of this alloy and performance are that the strict control by alloy obtains.Especially, the combination add-on of niobium and tin should remain in given range.Aluminium, molybdenum, silicon and oxygen also should be controlled in given range, to obtain the combination of good character.Impurity such as zirconium, iron, nickel and chromium should remain on quite low level.
The oxidation test result of the various titanium alloys of table 1-
Figure BDA00003536752500151
Figure BDA00003536752500161
The mechanical property test result of the various titanium alloys of table 2-
Figure BDA00003536752500162
The creep rupture property detection result of the various titanium alloys of table 3
Figure BDA00003536752500163
The weightening finish of each tkh titanium alloy of table 4 and α phase layer depth
Figure BDA00003536752500172
The oxidation test result of table 5-Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy
Figure BDA00003536752500173
The mechanical property test result of table 6-Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy
Figure BDA00003536752500174
Figure BDA00003536752500181
The creep rupture character of table 7-Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy
Figure BDA00003536752500182
Attention: 100* represents that fracture event is greater than 100 hours.
The room temperature tensile character (removal zone of oxidation) of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy after the hot irradiation of table 8-
Figure BDA00003536752500191
The room temperature tensile character (with zone of oxidation) of Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy after the hot irradiation of table 9-
The hyperbolic ductility of table 10-Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy
Figure BDA00003536752500193
Figure BDA00003536752500201
The thermoforming character (strain rate effect rate tension character, 0.01/ second) of table 11-Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy
Temperature, ℃ 788 816 843 871 927
True stress under 0.2 true strain, MPa 348 293 236 187 110
Elongation, % 91 95 190 200 230
Superplastic forming character (Strain rate, the 3x10 of table 12-Ti-6Al-4Sn-3Nb-0.5Mo-0.3Si alloy -4/ second)
SPF temperature, ℃ 927 940 954 968
Stress under 0.2 true strain, MPa 30 25 20 17
Stress under 1.1 true strains, MPa 37 33 26 25
General extension, % 400 460 360 340
Room temperature shown in table 2,6,8 and 9 (approximately 25 ℃) Elongation test is to carry out according to ASTM E8-11 standard (standard test methods of metallic substance tension test); Drawing by high temperature test shown in table 2,6,8 and 9 is to carry out according to ASTM E21-09 standard (standard test methods of the high temperature tension test of metallic substance); Thermoforming character test shown in table 11 is carried out according to ASTM E21-09 standard; Creep rupture test shown in table 3 and table 7 is to carry out according to ASTM139-11 standard (standard test methods of metallic substance conduction creep, creep rupture and stress cracking test); Hyperbolic test shown in table 10 is to carry out according to ASTM E290-09 standard (standard test methods of ductility material bending test); Superplastic forming test shown in Figure 12 is to carry out according to ASTM E2448-08 standard (measuring the standard test methods of the superplasticity property of metal plate layer material); The sample using in oxidation test (table 1,4 and 5) about weightening finish and α phase layer depth is about 2mm x10mmx50mm.
Usually, this titanium alloy, at least 600,650, has excellent oxidation-resistance, high strength and creep resistance under the high temperature of 700 and 750 ℃, also have good cold/thermoforming ability, good superplastic forming performance and good weldability.These titanium alloys can be as the structure unit with oxidation-resistance at high temperature, rotproofness, high strength and lighter weight, such as parts (housing, blade and blade) and the trolley part (valve) of body parts (heat shield, plug nozzle etc.), aircraft engine.
These alloys can also be used to form multiple member, article or parts, and especially those need at high temperature have high-intensity parts.Although this alloy is very useful under the high temperature of for example 650 ℃, 700 ℃ or 750 ℃, this alloy can also, at 600 ℃ (1112 °F) in low a little or lower temperature, provide significant advantage.Namely, although other titanium alloys are very applicable under lower high temperature, this alloy at these temperature, also provide at least part of characteristic previously discussed aspect significant advantage.
Fig. 5～8 show some parts that can be formed by this titanium alloy.With reference to Fig. 5, show aircraft 1, it has fuselage 2, wing 4 and the hanger 8 by is separately arranged on the gas-turbine 6 on aircraft wing 4.Fig. 6 shows hanger 8 and is fixed on wing 4 and to downward-extension, from hanger 8, is fixed with forward aircraft engine 6, and it is fixed on hanger 8 and from it to downward-extension.More particularly, hanger 8 has anterior 10 and afterbody or caudad 12, thereby the top of afterbody 12 is fixed on the bottom of wing 4 and the top that anterior 10 bottom is fixed on engine 6.Usually, the hanger member of the engine component of engine 6 or hanger 8 can be formed by alloy of the present invention, includes but are not limited to described in detail below.
Engine 6 can comprise: nacelle 14, and it has the front end that limits inlet mouth 16; Motor body 18; Compressor section 20, can comprise the low pressure compressor 22 with low pressure rotary compressor blade 24 and the high pressure compressor 26 with high-pressure rotary compressor blade 28; The wing of static state or stator or blade 30; Combustion chamber 32; Turbine part 34, can comprise the turbine 36 with revolving wormgear blade 38; Exhaust system, comprises that exhaust nozzle or nozzle assembly 40 and exhaust block up 42, and various fastening piece, for example high temperature fastening piece.Blade 30 can be in compressor section 20 and/or in turbine part 34.Caudad hanger 8 comprises various caudad hanger member and the multiple fastening pieces with the heat shield 44 arranging along hanger 8 bottoms.United States Patent (USP) 7,943,227 disclose a kind of heat shield 44, as the representative of heat shield type, at this, are incorporated to by reference this specification sheets.U.S. Patent Application Publication 2011/0155847 discloses another kind of such heat shield, and also referred to as the nose cone of caudad hanger, at this, it is to be also incorporated to by reference this specification sheets.
The fastening piece of engine 6 and/or hanger 8 or clamp structure can be represented by the fastening piece shown in Fig. 7 and/or clamp structure, its especially a kind of threaded fastener being formed by screw 46, nut 48 and packing ring 50.Fastening piece shown in Fig. 7 and/or clamp structure are simplification and general, and are used for representing fastening piece and the clamp structure of multiple known other types.This fastening piece or member can for example be used in aircraft engine or the more common place in aircraft.This fastening piece or member also can be used for various hot environments, and the engine of other types for example, as in automobile or other vehicles or the oil engine being used for other purposes.The fastening piece and the member that by this titanium alloy, are formed can be used under low temperature environment, but it provides particularly favourable aspect high-intensity fastening piece under the hot environment of for example temperature previously discussed.
As everyone knows, aircraft engine 6 is a kind of forms of fuels and energy engine, and it can produce a large amount of heat at run duration.Although engine 6 is that it also can represent other fuels and energy engine as shown in the gas turbine engine of aircraft, any oil engine for example, it can be reciprocator, as the engine of automobile.So this titanium alloy can be used to form the member of this fuels and energy engine, and especially favourable concerning being more subject to the high-temperature component of oxidation affects or member.
Fig. 8 shows a kind of this member occurring with automotive engine valves 52 forms, and it comprises stem portion (stem) 54, fillet part 56 and valve head 58.Fillet part 56 dwindles gradually and caves inward to stem portion 54 from valve head 58.Stem portion 54 ends at the end 60 back to 58.Stem portion 54 is close to end 60, limits and keeps groove 62, for receiving the guard ring of the spring of engine valve.58 have for being resisted against the valve-seat face 64 of the valve seating of engine.United States Patent (USP) 6,718,932 disclose the engine poppetvalve such as valve 58, and it is incorporated in this specification sheets at this by reference.
Engine 6 can be as previously mentioned, typical example is as gas turbine engine or reciprocator or any fuels and energy engine, also can represent more widely a kind of machine comprising by the member of making under alloy of the present invention, result is, move this machine and will produce heat, thereby make member at least 600 ℃, 650 ℃, under the operating temperature of 700 ℃ or 750 ℃, continue to keep at least 1/2 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or longer, as in the relevant form providing at this, record for as described in keep 24 hours at temperature, the time length of waiting for 48 hours.Machine can also operate to reach these temperature according to above-mentioned number of times or time length, but needn't be in a continuous manner, but carries out in intermittent mode, thereby total time cycle or time length can for example equal the example specific time length described above.In either case, member will be exposed in air conventionally at described temperature, and thus, the total duration that contacts oxygen under such high temperature can be continuous or step equally.
Applicant has the right to advocate the protection to this alloy, the parts that formed by it or methods involving of mode to increase any numerical value increment in this record; the increment of these numerical value includes but not limited to; for example, form the per-cent of the element of this alloy, cited temperature and time, gain in weight, α phase layer depth, extensibility etc.
In detailed description above, use some term be for simplicity, clear, easy to understand.Because these terms are the objects that are used as narration, and should be explained synoptically, exceed thus in non-essential restriction beyond the needs of prior art will can not be implied in.
In addition, the description of the preferred embodiments of the present invention and diagram are only examples, and the present invention is not limited in the detail that illustrates or describe.

Claims (15)

1. high-temperature titanium alloy, mainly consists of the following composition:
The aluminium of 4.5～7.5wt%;
The tin of 2.0～8.0wt%;
The niobium of 1.5～6.5wt%;
The molybdenum of 0.1～2.5wt%;
The silicon of 0.1～0.6wt%; With
Surplus titanium.
2. alloy according to claim 1, wherein, aluminium content is 5.5～6.5wt%; Tin content is 3.5～4.5wt%; Content of niobium is 2.75～3.25%; Molybdenum content is 0.5～0.8%; Silicone content is 0.30～0.45wt%; Oxygen level is 0.08～0.12wt%; Carbon content is 0.02～0.04wt%; And the content of zirconium, iron, nickel and chromium is respectively less than 0.1wt%.
3. alloy according to claim 1, wherein, described alloy comprises no more than 0.20% oxygen and no more than 0.10% carbon.
4. alloy according to claim 1, wherein, described alloy comprises zirconium and the vanadium of total content within the scope of 0.0～0.5wt%.
5. alloy according to claim 1, wherein, described alloy comprises content nickel, iron, chromium, copper and the magnesium of no more than 0.10wt% respectively.
6. alloy according to claim 1, wherein, described alloy comprises hafnium and the rhenium of total content within the scope of 0.0～0.3wt%.
7. alloy according to claim 1, wherein, described alloy has at least 260 ultimate tensile strength when the temperature of about 750 ℃.
8. alloy according to claim 1, wherein, described alloy has at least 150 yield strength when the temperature of about 750 ℃.
9. alloy according to claim 1, wherein, described alloy when the temperature of about 750 ℃, continue to remain on air in after 208 hours, the weightening finish of described alloy is for being no more than 2.00mg/cm 2.
10. alloy according to claim 1, wherein, described alloy at the temperature of about 750 ℃, continue to remain on air in after 208 hours, the α phase layer depth of described alloy is for being no more than about 100 microns.
11. alloys according to claim 1, wherein, described alloy at the temperature of about 750 ℃, be exposed to air in after 100 hours, while being in about 25 ℃ with respect to it, there is at least 2% percentage elongation.
12. alloys according to claim 1, wherein, described alloy is made at least part of of one of following parts: (a) aircraft engine nacelle, (b) aircraft engine shell, (c) the rotary compressor blade of aircraft engine, (d) blade of aircraft engine stator, (e) engine rotation formula turbine impellers, (f) gas discharge nozzle of aircraft engine, (g) exhaust plug of aircraft engine, (h) fastening piece of aircraft engine, and the (i) heat shield of engine hanger.
13. alloys according to claim 1, wherein, described alloy is made into the parts of oil engine or the parts of gas turbine engine.
14. alloys according to claim 13, wherein, described alloy is made into the parts of described oil engine; The parts of described oil engine are valves.
15. alloys according to claim 1, wherein, described alloy is made with the parts of the working temperature of at least about 600 ℃.
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US9957836B2 (en) 2018-05-01
CN108486409A (en) 2018-09-04

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